JP2003246988A - New dewaxing assistant - Google Patents
New dewaxing assistantInfo
- Publication number
- JP2003246988A JP2003246988A JP2002093268A JP2002093268A JP2003246988A JP 2003246988 A JP2003246988 A JP 2003246988A JP 2002093268 A JP2002093268 A JP 2002093268A JP 2002093268 A JP2002093268 A JP 2002093268A JP 2003246988 A JP2003246988 A JP 2003246988A
- Authority
- JP
- Japan
- Prior art keywords
- wax
- dewaxing
- containing hydrocarbon
- hydrocarbon oil
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 52
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 52
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000014509 gene expression Effects 0.000 claims 1
- 230000020169 heat generation Effects 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 239000001993 wax Substances 0.000 description 67
- 239000003921 oil Substances 0.000 description 61
- 239000012752 auxiliary agent Substances 0.000 description 40
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000010998 test method Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- -1 SUS as well as iron Chemical class 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000013213 extrapolation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
- C10G73/06—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of solvents
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、潤滑油製造工程に
おいて溶剤脱ロウ法で使用する脱ロウ助剤に関するもの
であり、特に脱ロウ工程において含ロウ炭化水素油と脱
ロウ助剤を脱ロウ溶剤に溶解させて冷却し、含ロウ炭化
水素油に存在するワックスを析出させ、析出したワック
スを液体／固体分離方法により分離を行ない、脱ロウ油
を生成させる溶剤脱ロウ法で使用する脱ロウ助剤に関す
るものである。TECHNICAL FIELD The present invention relates to a dewaxing auxiliary agent used in a solvent dewaxing method in a lubricating oil production process, and particularly to dewaxing wax-containing hydrocarbon oil and dewaxing auxiliary agent in the dewaxing step. Dewaxing used in a solvent dewaxing method in which a wax present in wax-containing hydrocarbon oil is dissolved in a solvent and cooled, and the deposited wax is separated by a liquid / solid separation method to produce a dewaxed oil. It concerns an auxiliary agent.
【０００２】[0002]
【従来の技術】一般に原油から炭化水素油を製造するに
は、まず原油を常圧蒸留し、その残油を更に減圧蒸留す
ることにより、低粘度から高粘度までの各種含ロウ炭化
水素油及び減圧蒸留残油に分離する。また、減圧蒸留残
油からこれらをさらに溶剤脱れき処理し、アスファルト
分を除去することにより、最も粘度の高い含ロウ炭化水
素油であるブライトストックを製造することが出来る。2. Description of the Related Art Generally, in order to produce a hydrocarbon oil from a crude oil, first, the crude oil is distilled under atmospheric pressure, and the residual oil is further distilled under reduced pressure to obtain various wax-containing hydrocarbon oils of low to high viscosity. Separate into vacuum distillation bottoms. Further, bright stock, which is a wax-containing hydrocarbon oil having the highest viscosity, can be produced by subjecting these to a solvent deasphalting treatment from the vacuum distillation residual oil to remove the asphalt content.
【０００３】こうして得られた各種粘度の含ロウ炭化水
素油は、溶剤抽出、水素化精製及び脱ロウの組み合わ
せ、又は水素化分解、溶剤抽出、水素化精製及び脱ロウ
の組み合わせ等、一連の処理工程にかけられ、炭化水素
油となる。The thus obtained wax-containing hydrocarbon oil of various viscosities is subjected to a series of treatments such as a combination of solvent extraction, hydrorefining and dewaxing, or a combination of hydrocracking, solvent extraction, hydrorefining and dewaxing. Processed to hydrocarbon oil.
【０００４】これら上記の製造工程のうち脱ロウ工程
は、含ロウ炭化水素油中のロウ分を除去し、低流動点の
炭化水素油を製造する工程を言う。The dewaxing step among the above-mentioned production steps is a step of producing a low pour point hydrocarbon oil by removing the wax content in the wax-containing hydrocarbon oil.
【０００５】工業的に脱ロウ工程を行なう場合は途中プ
レスろ過を行なう時がある。この場合、含ロウ炭化水素
油を溶剤不存在下で冷却しワックスを析出させて、これ
をプレスろ過する。一般的にプレスろ過工程を含む脱ロ
ウ法では、粘度による制限のためライト系含ロウ炭化水
素油しか処理できない。そのため、一般的には、ライト
系、ヘビー系等の処理が可能な溶剤脱ロウ法が用いられ
る。溶剤脱ロウ法は、含ロウ炭化水素油，脱ロウ溶剤及
び脱ロウ助剤を溶解し冷却を行ないながらワックスを析
出させ、スラリーを形成させる。このスラリーを固体／
液体分離機（ろ過、遠心分離等）に供給し、分離後脱ロ
ウ溶剤を取り除き脱ロウ油を得る。When the dewaxing process is industrially performed, press filtration may be performed on the way. In this case, the wax-containing hydrocarbon oil is cooled in the absence of a solvent to precipitate a wax, which is press-filtered. Generally, in the dewaxing method including the press filtration step, only light wax wax-containing hydrocarbon oil can be processed due to the limitation due to viscosity. Therefore, generally, a solvent dewaxing method capable of performing light type treatment, heavy type treatment and the like is used. In the solvent dewaxing method, a wax-containing hydrocarbon oil, a dewaxing solvent, and a dewaxing auxiliary agent are dissolved, and wax is precipitated while cooling to form a slurry. This slurry is solid /
It is supplied to a liquid separator (filtration, centrifugal separation, etc.), and after separation, the dewaxing solvent is removed to obtain dewaxed oil.
【０００６】溶剤脱ロウ法に使用する脱ロウ溶剤は、炭
化水素類（プロパン、プロピレン、ブタン、ペンタンな
ど）、ケトン類（アセトン、メチルエチルケトン（ＭＥ
Ｋ）、メチルイソブチルケトン（ＭＩＢＫ）及びその混
合物）、芳香族炭化水素類（ベンゼン、トルエン、キシ
レン）、ケトン類と芳香族炭化水素との混合物（ＭＥＫ
／トルエン及びアセトン／ベンゼン）がある。The dewaxing solvent used in the solvent dewaxing method includes hydrocarbons (propane, propylene, butane, pentane, etc.), ketones (acetone, methyl ethyl ketone (ME).
K), methyl isobutyl ketone (MIBK) and mixtures thereof), aromatic hydrocarbons (benzene, toluene, xylene), mixtures of ketones and aromatic hydrocarbons (MEK)
/ Toluene and acetone / benzene).
【０００７】溶剤脱ロウ工程で処理能力を制限する因子
にスラリーからのワックスろ過速度がある、この速度は
析出したワックスの結晶構造により影響を受ける。析出
したワックスの結晶構造は、脱ロウ工程における操作条
件によって影響される。特に冷却速度、攪拌速度、冷却
温度等条件の変化により同じ含ロウ炭化水素油でも析出
したワックスの寸法、結晶構造、結晶中における油等の
状態は著しく変化し、ろ過速度及び脱ロウ油の収率に影
響を及ぼす。特に含ロウ炭化水素油がブライトストック
の場合、ワックス結晶は微細であるためろ過による分離
において、ろ過速度低下、脱ロウ油収率の減少、微細結
晶の通過による脱ロウ油の流動点上昇、フィルターの目
詰まり等、度々トラブルを生じてきた。ろ過速度及び脱
ロウ油収率向上には種々のプロセス上の改良が行なわれ
ているが容易な操作でかつ効果の大きな方法に脱ロウ助
剤を添加する方法が実施されている。特にプロパン脱ロ
ウのような自己冷却式の脱ロウ法では脱ロウ助剤を添加
することが必須とされてきた。A factor limiting the throughput in the solvent dewaxing step is the wax filtration rate from the slurry, which is affected by the crystal structure of the precipitated wax. The crystal structure of the deposited wax is influenced by the operating conditions in the dewaxing process. In particular, due to changes in conditions such as cooling rate, stirring rate and cooling temperature, the size, crystal structure and state of oil in the precipitated wax of the same wax-containing hydrocarbon oil significantly change. Affect the rate. In particular, when the wax-containing hydrocarbon oil is a bright stock, the wax crystals are fine, and therefore the separation of the wax by filtration reduces the filtration rate, reduces the dewaxed oil yield, increases the pour point of the dewaxed oil due to the passage of fine crystals, and filters the filter. Trouble has often occurred, such as clogging of. Although various process improvements have been made in order to improve the filtration rate and the dewaxed oil yield, a method of adding a dewaxing auxiliary agent has been carried out by an easy operation and a highly effective method. Particularly in a self-cooling type dewaxing method such as propane dewaxing, it has been essential to add a dewaxing aid.
【０００８】脱ロウ助剤には、これまで下記の技術が公
知の技術となっている。特公昭４５−１５３７９、特公
昭４９−２６９２２、特開昭５４−１１１０４には、エ
チレン酢酸ビニル共重合物とポリアルキルアクリレート
もしくは、ポリアルキルメタアクリレートとの混合使用
による効果が記載されている。特開昭４５−１５３７
９、特公昭４９−４６３６１、特開昭５３−１２９２０
２には、アルキルナフタレン縮合物、もしくはポリアル
キルメタアクリレートとの混合の使用よる効果が記載さ
れている。特開昭５３−１２１８０４、特開昭５３−１
２１８０３には、α−オレフィン重合体、またはα−オ
レフィンと酢酸ビニルとの共重合体の使用よる効果が記
載されている。特開昭４０−４２１０、特開昭５４−１
２３１０２、特開昭５７−３０７９２、特開平７−３１
６５６７には、ポリアルキルアクリレートの使用よる効
果が記載されている。特開昭５５−８９３９２には、ポ
リビニルピロリドンの使用よる効果が記載されている。
特開昭６０−２１７２１８、特開昭６１−２４７７９３
には、フマル酸ジアルキルと酢酸ビニルとの共重合体の
使用よる効果が記載されている。The following techniques have hitherto been known as dewaxing aids. JP-B-45-15379, JP-B-49-26922, and JP-A-54-11104 describe the effects of the mixed use of an ethylene vinyl acetate copolymer and a polyalkyl acrylate or a polyalkyl methacrylate. JP-A-45-1537
9, JP-B-49-46361, JP-A-53-12920
2 describes the effect of using an alkylnaphthalene condensate or a mixture with a polyalkylmethacrylate. JP-A-53-1212804 and JP-A-53-1
21803 describes the effect of using an α-olefin polymer or a copolymer of an α-olefin and vinyl acetate. JP-A-40-4210, JP-A-54-1
23102, JP-A-57-30792, JP-A-7-31.
6567 describes the effect of using polyalkyl acrylates. JP-A-55-89392 describes the effect of using polyvinylpyrrolidone.
JP-A-60-217218, JP-A-61-247793
Describes the effect of using a copolymer of dialkyl fumarate and vinyl acetate.
【０００９】これらの従来技術のうち、特公昭４９−２
６９２２、特開昭５４−１１１０４、特開昭５３−１２
１８０４、特開昭５３−１２１８０３、特開昭６０−２
１７２１８、特開昭６１−２４７７９３では反応性の二
重結合を持つ化合物（反応性モノマー）と酢酸ビニルと
の共重合物の脱ロウ助剤としての使用が示されている。
酢酸ビニル基をもつ化合物は、熱等により分解し、酢酸
を生成することがある。酢酸は、鉄はもとよりＳＵＳ等
の金属に対し腐食性もつため、装置に対する不安材料と
なる場合がある。Among these conventional techniques, Japanese Examined Patent Publication No. 49-2
6922, JP-A-54-11104, and JP-A-53-12
1804, JP-A-53-121803, JP-A-60-2
17218 and JP-A-61-247793 disclose the use of a copolymer of a compound having a reactive double bond (reactive monomer) and vinyl acetate as a dewaxing aid.
A compound having a vinyl acetate group may be decomposed by heat or the like to generate acetic acid. Since acetic acid is corrosive to metals such as SUS as well as iron, it may be a concern for the device.
【００１０】また、特開昭４５−１５３７９、特公昭４
９−４６３６１ではアルキルナフタレン縮合物の脱ロウ
助剤としての使用が示されている。アルキルナフタレン
縮合物は、一般に塩素化パラフィンを原料にし、フリー
デルクラフツ反応によって得られるため、これに含有さ
れる塩素分は皆無とはいえない。近年あらゆる分野で塩
素フリーの製品が強く望まれるようになってきている。In addition, JP-A-45-15379 and JP-B-4.
9-46361 shows the use of alkylnaphthalene condensates as dewaxing aids. The alkylnaphthalene condensate is generally obtained by the Friedel-Crafts reaction using chlorinated paraffin as a raw material, so that it cannot be said that the chlorine content contained therein is completely absent. In recent years, chlorine-free products have been strongly desired in all fields.
【００１１】加えて、従来技術に記載のポリアルキルア
クリレートの脱ロウ助剤としての使用では、実験室の検
討では良好な性能を示すが、冷却速度が３０℃／分以上
の速度で冷却される工程を含む実機での評価において
は、特にヘビー系の含ロウ炭化水素油に対し充分な効果
があるとは言えず、さらに有効な助剤が求められてい
る。In addition, the use of the polyalkyl acrylates described in the prior art as dewaxing aids gives good performance in laboratory studies, but at a cooling rate of 30 ° C./min or more. In the evaluation in the actual machine including the process, it cannot be said that the wax-containing hydrocarbon oil of heavy type has a sufficient effect, and more effective auxiliary agents are required.
【００１２】[0012]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、従来技術で記載した脱ロウ助剤を用いた脱
ロウ方法では含ロウ炭化水素油の種類により汎用性がな
く、又はこれらの化合物が構造上・製造上回避すること
ができない短所（塩素を含有していること、分解時の生
成物が装置を腐食すること等）が存在することにある。
つまり、従来技術の助剤を用いた脱ロウ方法、例えば従
来からあるポリアルキルメタクリレートの使用では、単
独でライト系，ヘビー系含ロウ炭化水素油に効果が認め
られるものではなく、このため製造上塩素化合物を含有
することを回避できないアルキルナフタレン縮合物また
は構造上分解時に低分子酸を遊離する可能性のある反応
性モノマー／酢酸ビニル共重合物の使用が必要になって
しまう。The problem to be solved by the present invention is that the dewaxing method using the dewaxing aid described in the prior art is not versatile depending on the type of wax-containing hydrocarbon oil, or There is a drawback in that the compound (1) cannot be avoided in terms of structure and manufacturing (containing chlorine, the product at the time of decomposition corrodes the equipment, etc.).
In other words, the conventional dewaxing method using an auxiliary agent, for example, the conventional use of polyalkylmethacrylate does not show any effect on the light type and heavy type wax-containing hydrocarbon oils alone. The use of an alkylnaphthalene condensate, which cannot avoid avoiding the inclusion of chlorine compounds, or a reactive monomer / vinyl acetate copolymer, which structurally may release a low-molecular acid upon decomposition, becomes necessary.
【００１３】[0013]
【課題を解決するための手段】本発明者は、これら上記
の問題を解決するため鋭意検討した結果、溶剤脱ロウ法
において、実験室スケールの評価に実装置と同様のプレ
チリング工程（急冷工程）を加える事により、冷却速度
が３０℃／分以上の速度で冷却される工程を含む実機で
の評価と相関のある脱ろう助剤を見いだす事ができた。
それらはさらに、どの含ロウ炭化水素油に対しても効果
を示し、従来の脱ろう助剤よりろ過速度・脱ロウ油収率
を向上させる事ができる、という発見に達した。The present inventor has conducted extensive studies as a solution to these problems, and as a result, in the solvent dewaxing method, the same prepiling step (quenching step) as in an actual apparatus was used for laboratory scale evaluation. It was possible to find a dewaxing aid that correlates with the evaluation in an actual machine including the step of cooling at a cooling rate of 30 ° C./min or more by adding.
Furthermore, they have found that they have an effect on any wax-containing hydrocarbon oil and can improve the filtration rate and the dewaxed oil yield more than conventional dewaxing aids.
【００１４】すなわち本発明は、含ロウ炭化水素油及び
脱ロウ助剤を脱ロウ溶剤に溶解し、冷却することにより
ワックスを析出させ、析出したワックスを液体／固体分
離方法により除去し脱ロウ油を得るという脱ロウ方法に
おいて、下記の条件を満たすものであって、炭素数１０
〜３０のアルキル基を有する、少なくとも２種類のポリ
アルキル（メタ）アクリレート（Ａ），（Ｂ）の混合物
であり、かつ（Ａ）／（Ｂ）の重量比が３／９７〜９７
／３であることを特徴とした脱ロウ助剤である。この脱
ろう助剤は、含ロウ炭化水素油に（Ａ），（Ｂ）それぞ
れを添加したときに、示差走査熱量計により３０℃／分
の急冷で測定される、発熱開始温度が脱ロウ助剤を添加
しないときの含ロウ炭化水素油の発熱開始温度（Ｔａ）
と（Ａ）（０．２５％）を添加したときの含ロウ炭化水
素油の発熱開始温度（ｔａ）および（Ｂ）（０．２５
％）を添加したときの含ロウ炭化水素油の発熱開始温度
（ｔｂ）が下記の式（１）及び（２）の条件を満たす。
−４．０℃＋Ｔａ≦ｔａ≦−１．０℃＋Ｔａ （１）
Ｔａ≦ｔｂ≦４．０℃＋Ｔａ （２）That is, according to the present invention, a wax-containing hydrocarbon oil and a dewaxing aid are dissolved in a dewaxing solvent and cooled to precipitate a wax, and the deposited wax is removed by a liquid / solid separation method to remove the dewaxed oil. In the dewaxing method of obtaining, the following conditions are satisfied and the number of carbon atoms is 10:
A mixture of at least two polyalkyl (meth) acrylates (A) and (B) having 30 to 30 alkyl groups and a weight ratio of (A) / (B) of 3 / 97-97.
It is a dewaxing aid characterized by being / 3. This dewaxing aid has an exothermic starting temperature measured by quenching with a differential scanning calorimeter at 30 ° C./min when each of (A) and (B) is added to the wax-containing hydrocarbon oil. Exothermic onset temperature (Ta) of wax-containing hydrocarbon oil when no agent is added
And (A) (0.25%) are added, the exothermic onset temperature (ta) of the wax-containing hydrocarbon oil and (B) (0.25
%) Is added, the heat generation start temperature (tb) of the wax-containing hydrocarbon oil satisfies the conditions of the following formulas (1) and (2). −4.0 ° C. + Ta ≦ ta ≦ −1.0 ° C. + Ta (1) Ta ≦ tb ≦ 4.0 ° C. + Ta (2)
【００１５】本発明の脱ロウ助剤が効果を示す脱ロウ方
法は、冷却速度が３０℃／分以上の速度で冷却される工
程を含む溶剤脱ロウ法である。たとえば、常温で気体の
炭化水素類（プロパン、プロピレン、ブタン、ブテンな
ど）を使用する脱ロウ方法、ケトン類（アセトン、メチ
ルエチルケトン（ＭＥＫ）、メチルイソブチルケトン
（ＭＩＢＫ）等及びその混合物）を使用する脱ロウ方
法、芳香族炭化水素類（ベンゼン、トルエン、キシレン
等）を使用する脱ロウ方法、ケトン類と芳香族炭化水素
との混合物（ＭＥＫ／トルエン、アセトン／ベンゼン
等）を使用する脱ロウ方法等である。The dewaxing method in which the dewaxing aid of the present invention is effective is a solvent dewaxing method including a step of cooling at a cooling rate of 30 ° C./minute or more. For example, a dewaxing method using hydrocarbons (propane, propylene, butane, butene, etc.) that are gaseous at room temperature, ketones (acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), etc. and mixtures thereof) are used. Dewaxing method, dewaxing method using aromatic hydrocarbons (benzene, toluene, xylene, etc.), dewaxing method using a mixture of ketones and aromatic hydrocarbons (MEK / toluene, acetone / benzene, etc.) Etc.
【００１６】（Ａ），（Ｂ）はアルキル基の炭素数が１
０〜３０のアルキル（メタ）アクリレートであるが、こ
れは単一であっても混合物であっても良い。一般的な例
としては、デシル（メタ）アクリレート、ウンデシル
（メタ）アクリレート、ドデシル（メタ）アクリレー
ト、トリデシル（メタ）アクリレート、テトラデシル
（メタ）アクレート、ペンタデシル（メタ）アクリレー
ト、ヘキサデシル（メタ）アクリレート、ヘプタデシル
（メタ）アクリレート、オクタデシル（メタ）アクリレ
ート、ノナデシル（メタ）アクレート、エイコシル（メ
タ）アクレート、ドコシルアクリレート等とこれらの混
合物があげられるIn (A) and (B), the carbon number of the alkyl group is 1
It is 0 to 30 alkyl (meth) acrylates, which may be single or a mixture. Common examples are decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl. (Meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl acrylate and the like, and mixtures thereof.
【００１７】（Ａ）と（Ｂ）の存在質量比率は、
（Ａ）：（Ｂ）で示した時３：９７〜９７：３の範囲内
であることが、性能上望ましい。The existing mass ratio of (A) and (B) is
(A): It is desirable in terms of performance that the ratio is within the range of 3:97 to 97: 3 when represented by (B).
【００１８】さらに、（Ａ）は炭素数１０〜２０のアル
キル鎖長を有し重量平均分子量１０，０００〜８００，
０００であることが好ましい。また、（Ｂ）は炭素数１
６〜３０のアルキル鎖長を有し重量平均分子量１０，０
００〜８００，０００であることが好ましい。重量平均
分子量が１０，０００より小さい時は、脱ロウ助剤とし
ての性能が発揮できない場合があり、重量平均分子量が
８００，０００より大きい時は、含脱ロウ炭化水素油ま
たは脱ロウ溶剤への溶解性が悪化する。Further, (A) has an alkyl chain length of 10 to 20 carbon atoms and a weight average molecular weight of 10,000 to 800,
It is preferably 000. Also, (B) has 1 carbon atom.
Weight average molecular weight 10,0 having an alkyl chain length of 6 to 30
It is preferably from 00 to 800,000. When the weight average molecular weight is less than 10,000, the performance as a dewaxing aid may not be exerted, and when the weight average molecular weight is more than 800,000, the dewaxed hydrocarbon oil or dewaxing solvent may not be treated. Solubility deteriorates.
【００１９】（Ａ），（Ｂ）の合成は、従来技術による
任意の方法である。例えば、炭素数１０〜３０のアルコ
ールとメタクリル酸もしくはアクリル酸をエステル化反
応、これら過酸化物またはアゾビス系の化合物を開始剤
として用いるラジカル重合や、加熱による熱重合によっ
て得ることも可能である。The synthesis of (A) and (B) is any conventional method. For example, it can be obtained by esterification reaction of an alcohol having 10 to 30 carbon atoms with methacrylic acid or acrylic acid, radical polymerization using these peroxides or azobis compounds as an initiator, or thermal polymerization by heating.
【００２０】尚、本発明に関する脱ロウ助剤は、本発明
の効果を損なわない範囲で他の成分を添加しても良い。
脱ロウ性能上（ろ過速度、脱ロウ油収率向上の点で）併
用可能と考えられるものとしては、ポリアルキルアクリ
レート、ポリアルキルメタクリレート、アルキルアクリ
レートとアルキルメタクリレートのコポリマー、アルキ
ルナフタレン縮合物、エチレンと酢酸ビニルの共重合物
等が考えられる。The dewaxing aid of the present invention may contain other components as long as the effects of the present invention are not impaired.
In terms of dewaxing performance (in terms of filtration rate and improvement of dewaxed oil yield), it is considered that polyalkyl acrylate, polyalkyl methacrylate, copolymer of alkyl acrylate and alkyl methacrylate, alkylnaphthalene condensate, ethylene A vinyl acetate copolymer or the like is considered.
【００２１】[0021]
【発明の実施の形態】含ロウ炭化水素油を脱ロウ溶剤に
溶かし本発明の脱ロウ助剤を添加し均一にし加熱する。
次いで、混合物を所定の温度まで冷却する、この冷却に
おいて析出ワックス、脱ロウ油、脱ロウ溶剤、脱ロウ助
剤から成るスラリーを生成させ、次いでスラリーをろ過
によりワックス分離を行ない、脱ロウ溶剤を除去するこ
とにより脱ロウ油を得る。この時のろ過速度、脱ロウ油
収率を測定し脱ロウ助剤の性能を評価した。BEST MODE FOR CARRYING OUT THE INVENTION A wax-containing hydrocarbon oil is dissolved in a dewaxing solvent and the dewaxing aid of the present invention is added to make it uniform and heated.
Then, the mixture is cooled to a predetermined temperature. In this cooling, a slurry consisting of precipitated wax, dewaxing oil, dewaxing solvent, and dewaxing aid is formed, and then the slurry is separated by wax to remove the dewaxing solvent. Dewaxed oil is obtained by removing. The filtration rate and the dewaxing oil yield at this time were measured to evaluate the performance of the dewaxing aid.
【００２２】示差走査熱量計による発熱開始温度の測定
は、セイコーインスツルメンツ（株）社製熱分析装置Ｄ
ＳＣ６２００を使用し、ポリ（メタ）アクリレート０．
２５重量％を含ロウ炭化水素油に添加し溶解混合を行な
い、この混合物を５ｍｇ採取し、１４０℃から−３０℃
まで３０℃／分の冷却速度で冷却した時、外挿により発
熱が始まった温度を発熱開始温度とした。The heat generation start temperature is measured by a differential scanning calorimeter by a thermal analyzer D manufactured by Seiko Instruments Inc.
SC6200, poly (meth) acrylate 0.
25% by weight was added to wax-containing hydrocarbon oil and dissolved and mixed, and 5 mg of this mixture was sampled from 140 ° C to -30 ° C.
The temperature at which heat generation started by extrapolation when cooled at a cooling rate of 30 ° C./min was taken as the heat generation start temperature.
【００２３】[0023]
【実施例】以下に（Ａ）、（Ｂ）の合成例、実施例、試
験方法をあげて本発明を説明するが、本発明はこれらの
（Ａ）、（Ｂ）の合成例、実施例、試験方法に限定され
るものではない。EXAMPLES The present invention will be described below with reference to synthetic examples, examples and test methods of (A) and (B). The present invention is based on the synthetic examples and examples of these (A) and (B). The test method is not limited.
【００２４】[0024]
【合成例】合成例１
炭素数１２〜１８（Ｃ１２＝１５％，Ｃ１４＝１８％，
Ｃ１６＝２５％，Ｃ１８＝４２％）のアルキルメタアク
リレート４０部と鉱油６０部を攪拌装置、窒素吹き込み
管、温度計、コンデンサーを備えたフラスコに入れ、３
時間十分に窒素置換を行ない、開始剤を添加し、１００
℃に加熱し、同温度で８時間熟成することにより、重量
平均分子量４０万のポリアルキルメタクリレートを得
た。この操作によって得られた化合物を助剤（１）とし
た。[Synthesis Example] Synthesis Example 1 C12 to C18 (C12 = 15%, C14 = 18%,
40 parts of alkylmethacrylate (C16 = 25%, C18 = 42%) and 60 parts of mineral oil were placed in a flask equipped with a stirrer, a nitrogen blowing tube, a thermometer, and a condenser.
Sufficiently perform nitrogen substitution for a time, add an initiator, and
By heating to 0 ° C. and aging at the same temperature for 8 hours, a polyalkyl methacrylate having a weight average molecular weight of 400,000 was obtained. The compound obtained by this operation was used as an auxiliary agent (1).
【００２５】合成例２
炭素数１８〜２２（Ｃ１８＝４３％，Ｃ２０＝１１％，
Ｃ２２＝４４％）のアルキルアクリレート４０部と鉱油
６０部を攪拌装置、窒素吹き込み管、温度計、コンデン
サーを備えたフラスコに入れ、３時間十分に窒素置換を
行ない、開始剤を添加し、１００℃に加熱し、同温度で
８時間熟成することにより、重量平均分子量４０万のポ
リアルキルアクリレートを得た。この操作によって得ら
れた化合物を助剤（２）とした。Synthesis Example 2 18 to 22 carbon atoms (C18 = 43%, C20 = 11%,
(C22 = 44%) Alkyl acrylate (40 parts) and mineral oil (60 parts) are placed in a flask equipped with a stirrer, a nitrogen blowing tube, a thermometer, and a condenser, and the nitrogen is sufficiently replaced for 3 hours. The mixture was heated to 1, and aged at the same temperature for 8 hours to obtain a polyalkyl acrylate having a weight average molecular weight of 400,000. The compound obtained by this operation was used as an auxiliary agent (2).
【００２６】合成例３
炭素数６〜１０（Ｃ６＝５％，Ｃ８＝７５％，Ｃ１０＝
２０％）のアルキルメタアクリレート４０部と鉱油６０
部を攪拌装置、窒素吹き込み管、温度計、コンデンサー
を備えたフラスコに入れ、３時間十分に窒素置換を行な
い、開始剤を添加し、１００℃に加熱し、同温度で８時
間熟成することにより、重量平均分子量４０万のポリア
ルキルメタクリレートを得た。この操作によって得られ
た化合物を助剤（３）とした。Synthesis Example 3 Carbon number 6 to 10 (C6 = 5%, C8 = 75%, C10 =
20%) 40 parts of alkyl methacrylate and 60 parts of mineral oil
Part was placed in a flask equipped with a stirrer, a nitrogen blowing tube, a thermometer, and a condenser, and nitrogen replacement was sufficiently performed for 3 hours, an initiator was added, and the mixture was heated to 100 ° C. and aged for 8 hours at the same temperature. A polyalkyl methacrylate having a weight average molecular weight of 400,000 was obtained. The compound obtained by this operation was used as an auxiliary agent (3).
【００２７】合成例４
炭素数１２〜１５（Ｃ１２＝２０％，Ｃ１３＝３１％，
Ｃ１４＝３３％，Ｃ１５＝１６％）のアルキルアクリレ
ート４０部と鉱油６０部を攪拌装置、窒素吹き込み管、
温度計、コンデンサーを備えたフラスコに入れ、３時間
十分に窒素置換を行ない、開始剤を添加し、１００℃に
加熱し、同温度で８時間熟成することにより、重量平均
分子量４０万のポリアルキルアクリレートを得た。この
操作によって得られた化合物を助剤（４）とした。Synthesis Example 4 Carbon number 12 to 15 (C12 = 20%, C13 = 31%,
C14 = 33%, C15 = 16%) 40 parts of alkyl acrylate and 60 parts of mineral oil are stirred, a nitrogen blowing tube,
Put in a flask equipped with a thermometer and a condenser, perform nitrogen substitution for 3 hours, add an initiator, heat to 100 ° C., and age for 8 hours to give a polyalkyl having a weight average molecular weight of 400,000. An acrylate was obtained. The compound obtained by this operation was used as an auxiliary agent (4).
【００２８】各助剤の発熱開始温度測定方法
助剤をポリマー分で０．２５重量％になるようにを含ロ
ウ炭化水素油（発熱開始温度４６．７℃）に添加し溶解
混合を行ない、この混合物を５ｍｇ採取し、１４０℃か
ら−３０℃まで３０℃／分の冷却速度で冷却した時、外
挿により発熱が始まった温度を発熱開始温度とした。Method for measuring the exothermic onset temperature of each auxiliary agent The auxiliary agent was added to wax-containing hydrocarbon oil (exothermic onset temperature 46.7 ° C.) so that the polymer content was 0.25% by weight, and dissolved and mixed, When 5 mg of this mixture was sampled and cooled from 140 ° C. to −30 ° C. at a cooling rate of 30 ° C./min, the temperature at which heat generation started by extrapolation was taken as the heat generation start temperature.
【００２９】試験方法
含ロウ炭化水素油（ヘビー系、発熱開始温度４６．７
℃）をノルマルヘキサン（含ロウ炭化水素油に対し４．
０倍）に５０℃で加熱し溶解させ、そこへ、上記で合成
した脱ロウ助剤を加え攪拌しながら冷却速度３０℃／分
で３０℃まで冷却を行ないその後冷却速度２℃／分で−
４０℃まで冷却を行ない、その後ワックス、ノルマルヘ
キサン、脱ロウ油、脱ロウ助剤から成るスラリーを、ジ
ャケット付ブフナーロートに−４０℃の冷媒を循環さ
せ、−４０℃にて、６００ｍｍＨｇで減圧ろ過を行なっ
た。この時２分間で、ろ過されたろ液量を測定し、下記
の式からろ過速度を求めた。また得られたろ液と、ろ過
後ワックスの各々含有するノルマルヘキサンをエバポレ
ーターで減圧トッピングすることにより除去し、それぞ
れの重量を測定して、下記の式から脱ロウ油収率を求め
た。Test method Wax-containing hydrocarbon oil (heavy type, exothermic starting temperature 46.7)
C) to normal hexane (4.
(0 times) to dissolve at 50 ° C., add the dewaxing aid synthesized above, and stir to cool to 30 ° C. at a cooling rate of 30 ° C./min, and then at a cooling rate of 2 ° C./min.
After cooling to 40 ° C, a slurry consisting of wax, normal hexane, dewaxing oil, and dewaxing aid is circulated through a Buchner funnel with a jacket at a temperature of -40 ° C and filtered under reduced pressure at 600 mmHg at -40 ° C. Was done. At this time, the amount of filtered filtrate was measured for 2 minutes, and the filtration rate was calculated from the following formula. Further, the obtained filtrate and normal hexane contained in each wax after filtration were removed by vacuum topping with an evaporator, each weight was measured, and the dewaxed oil yield was determined from the following formula.
【００３０】ろ過速度の計算式（ｍｌ／ｓ・ｃｍ２）Formula for calculating filtration rate (ml / s · cm 2 ).
【数１】 [Equation 1]
【００３１】脱ロウ油収率の計算式（質量％）Dewaxed oil yield calculation formula (mass%)
【数２】 [Equation 2]
【００３２】実施例１
合成例１で得られた本発明の助剤（１）０．５０ｇと、
合成例２で得られた助剤（２）０．５０ｇを、加温しな
がらヘビー系含ロウ炭化水素油２００ｇにそれぞれ添加
・溶解させ、さらにノルマルヘキサン７００ｍｌを加え
て溶解させ、試験方法に従い試験を行なった。つまり、
本発明の助剤（１）と助剤（２）の添加量をヘビー系含
ロウ炭化水素油に対しそれぞれ０．５質量％（助剤の純
分換算で０．２０％）に設定し、試験を行なった。Example 1 0.50 g of the auxiliary agent (1) of the present invention obtained in Synthesis Example 1,
0.50 g of the auxiliary agent (2) obtained in Synthesis Example 2 was added and dissolved in 200 g of heavy wax wax-containing hydrocarbon oil while heating, and 700 ml of normal hexane was further added and dissolved, and tested according to the test method. Was done. That is,
The amount of each of the auxiliary agent (1) and the auxiliary agent (2) of the present invention is set to 0.5% by mass (0.20% in terms of pure amount of the auxiliary agent) with respect to the heavy type wax-containing hydrocarbon oil, The test was conducted.
【００３３】実施例２
合成例１で得られた本発明の助剤（１）０．９０ｇと合
成例２で得られた助剤（２）０．１０ｇを、加温しなが
らヘビー系含ロウ炭化水素油２００ｇにそれぞれ添加・
溶解させ、さらにノルマルヘキサン７００ｍｌを加えて
溶解させ、試験方法に従い試験を行なった。つまり、本
発明の助剤（１）と助剤（２）の添加量をヘビー系含ロ
ウ炭化水素油に対しそれぞれ０．５質量％（助剤の純分
換算で０．２０％）に設定し、試験を行なった。Example 2 0.90 g of the auxiliary agent (1) of the present invention obtained in Synthesis Example 1 and 0.10 g of the auxiliary agent (2) obtained in Synthesis Example 2 were heated and heated to a heavy wax-containing wax. Added to 200g of hydrocarbon oil
After dissolving, 700 ml of normal hexane was further added and dissolved, and the test was conducted according to the test method. That is, the amounts of the auxiliary agent (1) and the auxiliary agent (2) of the present invention are set to 0.5% by mass (0.20% in terms of the total amount of the auxiliary agent) based on the heavy wax wax-containing hydrocarbon oil. Then, the test was conducted.
【００３４】実施例３
合成例１で得られた本発明の助剤（１）０．１０ｇと合
成例２で得られた助剤（２）０．９０ｇを、加温しなが
らヘビー系含ロウ炭化水素油２００ｇにそれぞれ添加・
溶解させ、さらにノルマルヘキサン７００ｍｌを加えて
溶解させ、試験方法に従い試験を行なった。つまり、本
発明の助剤（１）と助剤（２）の添加量をヘビー系含ロ
ウ炭化水素油に対しそれぞれ０．５質量％（助剤の純分
換算で０．２０％）に設定し、試験を行なった。Example 3 0.10 g of the auxiliary (1) of the present invention obtained in Synthesis Example 1 and 0.90 g of the auxiliary (2) obtained in Synthesis Example 2 were heated and heated to a heavy wax-containing wax. Added to 200g of hydrocarbon oil
After dissolving, 700 ml of normal hexane was further added and dissolved, and the test was conducted according to the test method. That is, the amounts of the auxiliary agent (1) and the auxiliary agent (2) of the present invention are set to 0.5% by mass (0.20% in terms of the total amount of the auxiliary agent) based on the heavy wax wax-containing hydrocarbon oil. Then, the test was conducted.
【００３５】比較例１
合成例３で得られた助剤（３）０．５０ｇと合成例４で
得られた助剤（４）０．５０ｇを、加温しながらヘビー
系含ロウ炭化水素油２００ｇにそれぞれ添加・溶解さ
せ、さらにノルマルヘキサン７００ｍｌを加えて溶解さ
せ、試験方法に従い試験を行なった。つまり、助剤
（３）と助剤（４）の添加量をヘビー系含ロウ炭化水素
油に対しそれぞれ０．５質量％（助剤の純分換算で０．
２０％）に設定し、試験を行なった。Comparative Example 1 0.50 g of the auxiliary agent (3) obtained in Synthetic Example 3 and 0.50 g of the auxiliary agent (4) obtained in Synthetic Example 4 were heated and heated to a heavy wax wax-containing hydrocarbon oil. 200 g of each was added and dissolved, and 700 ml of normal hexane was added and dissolved, and the test was performed according to the test method. That is, the amount of each of the auxiliary agent (3) and the auxiliary agent (4) added to the heavy wax wax-containing hydrocarbon oil was 0.5% by mass (0.
20%) and tested.
【００３６】比較例２
合成例１で得られた本発明の助剤（１）と合成例４で得
られた助剤（３）０．５０ｇを、加温しながらライト
系、ヘビー系含ロウ炭化水素油２００ｇにそれぞれ添加
・溶解させ、さらにノルマルヘキサン７００ｍｌを加え
て溶解させ、試験方法に従い試験を行なった。つまり、
助剤（１）と助剤（３）の添加量をヘビー系含ロウ炭化
水素油に対しそれぞれ０．５質量％（助剤の純分換算で
０．２０％）に設定し、試験を行なった。COMPARATIVE EXAMPLE 2 0.50 g of the auxiliaries (1) of the present invention obtained in Synthesis Example 1 and 0.50 g of the auxiliaries (3) obtained in Synthesis Example 4 were heated and heated to a light or heavy wax-containing wax. Hydrocarbon oil (200 g) was added and dissolved, and normal hexane (700 ml) was added and dissolved, and the test was conducted according to the test method. That is,
The amount of each of the auxiliary agent (1) and the auxiliary agent (3) added was set to 0.5% by mass (0.20% in terms of the pure amount of the auxiliary agent) with respect to the heavy wax wax oil, and the test was conducted. It was
【００３７】比較例３
合成例２で得られた本発明の助剤（２）と合成例３で得
られた助剤（４）０．５０ｇを、加温しながらヘビー系
含ロウ炭化水素油２００ｇにそれぞれ添加・溶解させ、
さらにノルマルヘキサン７００ｍｌを加えて溶解させ、
試験方法に従い試験を行なった。つまり、助剤（２）と
助剤（４）０．３ｇの添加量をライト系、ヘビー系含ロ
ウ炭化水素油に対しそれぞれ０．５質量％（助剤の純分
換算で０．２０％）に設定し、試験を行なった。Comparative Example 3 A heavy wax-containing wax-containing hydrocarbon oil was added while warming 0.50 g of the auxiliary agent (2) of the present invention obtained in Synthesis Example 2 and the auxiliary agent (4) obtained in Synthesis Example 3. Add / dissolve in 200 g each,
Then add 700 ml of normal hexane to dissolve it,
The test was conducted according to the test method. That is, the amounts of 0.3 g of the auxiliary agent (2) and the auxiliary agent (4) added were 0.5% by mass (0.20% in terms of the total amount of the auxiliary agent) with respect to the light type and heavy type wax-containing hydrocarbon oils. ) And tested.
【００３８】比較例４
助剤を使用せずにヘビー系含ロウ炭化水素油について試
験を行なった。Comparative Example 4 A test was carried out on a heavy wax-containing hydrocarbon oil without using an auxiliary agent.
【００３９】以上の各助剤と含ロウ炭化水素油の混合物
の発熱開始温度を表１、使用例１〜３、比較例１〜４で
得られたヘビー系含ロウ炭化水素油に対する脱ロウ性能
を表２に示した。The exothermic starting temperature of the mixture of each auxiliary agent and the wax-containing hydrocarbon oil described above is shown in Table 1, the dewaxing performance for the heavy wax-containing hydrocarbon oils obtained in Use Examples 1 to 3 and Comparative Examples 1 to 4. Is shown in Table 2.
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【表２】 [Table 2]
【００４２】[0042]
【発明の効果】表２より明らかな様に、本発明品の脱ロ
ウ助剤を、急冷工程を含む脱ロウ工程において使用する
と、ろ過速度・脱ロウ油収率共に大幅に改善される。こ
れは本発明品による格別の効果である。As is clear from Table 2, when the dewaxing aid of the present invention is used in the dewaxing step including the quenching step, both the filtration rate and the dewaxed oil yield are significantly improved. This is a special effect of the product of the present invention.
Claims (2)
ウ溶剤に溶解し、冷却することによりワックスを析出さ
せ、析出したワックスを液体／固体分離方法により除去
し脱ロウ油を得るという脱ロウ方法において、下記の条
件を満たすものであって、炭素数１０〜３０のアルキル
基を有する、少なくとも２種類のポリアルキル（メタ）
アクリレート（Ａ），（Ｂ）の混合物であり、かつ
（Ａ）／（Ｂ）の重量比が３／９７〜９７／３であるこ
とを特徴とした脱ロウ助剤。この脱ろう助剤は、含ロウ
炭化水素油に（Ａ），（Ｂ）それぞれを添加したとき
に、示差走査熱量計により３０℃／分の急冷で測定され
る、発熱開始温度が脱ロウ助剤を添加しないときの含ロ
ウ炭化水素油の発熱開始温度（Ｔａ）と（Ａ）（０．２
５％）を添加したときの含ロウ炭化水素油の発熱開始温
度（ｔａ）および（Ｂ）（０．２５％）を添加したとき
の含ロウ炭化水素油の発熱開始温度（ｔｂ）が下記の式
（１）及び（２）の条件を満たす。 −４．０℃＋Ｔａ≦ｔａ≦−１．０℃＋Ｔａ （１） Ｔａ≦ｔｂ≦４．０℃＋Ｔａ （２）1. A wax-containing hydrocarbon oil and a dewaxing aid are dissolved in a dewaxing solvent and cooled to precipitate a wax, and the deposited wax is removed by a liquid / solid separation method to obtain a dewaxed oil. In the dewaxing method, at least two types of polyalkyl (meth) which satisfy the following conditions and have an alkyl group having 10 to 30 carbon atoms:
A dewaxing aid, which is a mixture of acrylates (A) and (B) and has a weight ratio of (A) / (B) of 3/97 to 97/3. This dewaxing aid has an exothermic starting temperature measured by quenching with a differential scanning calorimeter at 30 ° C./min when each of (A) and (B) is added to the wax-containing hydrocarbon oil. Exothermic onset temperature (Ta) and (A) (0.2) of wax-containing hydrocarbon oil when no agent is added.
(5%) is added to the wax-containing hydrocarbon oil when the exothermic start temperature (ta) and (B) (0.25%) of the wax-containing hydrocarbon oil when exothermic start temperature (tb) are as follows. The conditions of Expressions (1) and (2) are satisfied. −4.0 ° C. + Ta ≦ ta ≦ −1.0 ° C. + Ta (1) Ta ≦ tb ≦ 4.0 ° C. + Ta (2)
ロウ溶剤に溶解し、冷却することによりワックスを析出
させ、析出したワックスを液体／固体分離方法により除
去し脱ロウ油を得るという脱ロウ方法において、冷却時
の冷却速度が３０℃／分以上の速度で冷却される工程を
含む脱ロウ方法に使用されることを特徴とする請求項１
に記載の脱ロウ助剤。2. A wax-containing hydrocarbon oil and a dewaxing aid are dissolved in a dewaxing solvent and cooled to precipitate a wax, and the deposited wax is removed by a liquid / solid separation method to obtain a dewaxed oil. The dewaxing method is used in a dewaxing method including a step of cooling at a cooling rate of 30 ° C./minute or more during cooling.
Dewaxing aid described in.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002093268A JP3841404B2 (en) | 2002-02-22 | 2002-02-22 | New dewaxing aid |
| PCT/JP2002/011100 WO2003070858A1 (en) | 2002-02-22 | 2002-10-25 | Novel dewaxing aid |
| AU2002344578A AU2002344578A1 (en) | 2002-02-22 | 2002-10-25 | Novel dewaxing aid |
| EP02777955A EP1486553A4 (en) | 2002-02-22 | 2002-10-25 | Novel dewaxing aid |
| US10/504,685 US7388122B2 (en) | 2002-02-22 | 2002-10-25 | Dewaxing aid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002093268A JP3841404B2 (en) | 2002-02-22 | 2002-02-22 | New dewaxing aid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003246988A true JP2003246988A (en) | 2003-09-05 |
| JP3841404B2 JP3841404B2 (en) | 2006-11-01 |
Family
ID=27751371
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002093268A Expired - Lifetime JP3841404B2 (en) | 2002-02-22 | 2002-02-22 | New dewaxing aid |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US7388122B2 (en) |
| EP (1) | EP1486553A4 (en) |
| JP (1) | JP3841404B2 (en) |
| AU (1) | AU2002344578A1 (en) |
| WO (1) | WO2003070858A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002097478A (en) * | 2000-09-21 | 2002-04-02 | Toho Chem Ind Co Ltd | Novel dewaxing auxiliary |
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|---|---|---|---|---|
| DE102011003855A1 (en) * | 2011-02-09 | 2012-08-09 | Evonik Rohmax Additives Gmbh | Process for dewaxing mineral oil compositions |
| CN102757821B (en) * | 2011-04-28 | 2014-08-20 | 中国石油化工股份有限公司 | Solvent dewaxing method for low waxy hydrocarbon oil |
| CN102757820B (en) * | 2011-04-28 | 2014-08-20 | 中国石油化工股份有限公司 | Solvent dewaxing method for low waxy hydrocarbon oil |
| CN102952573B (en) * | 2011-08-25 | 2014-12-31 | 中国石油化工股份有限公司 | Solvent dewaxing method of low-wax content hydrocarbon oil |
| CN103789039B (en) * | 2012-11-05 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of solvent-dewaxing method |
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| US4594142A (en) * | 1985-04-25 | 1986-06-10 | Exxon Research And Engineering Co. | Dewaxing waxy hydrocarbon oils using di-alkyl fumarate-vinyl laurate copolymer dewaxing aids |
| US4728414A (en) * | 1986-11-21 | 1988-03-01 | Exxon Research And Engineering Company | Solvent dewaxing using combination poly (n-C24) alkylmethacrylate-poly (C8 -C20 alkyl (meth-) acrylate dewaxing aid |
| DE3933376A1 (en) * | 1989-10-06 | 1991-04-18 | Roehm Gmbh | METHOD FOR DEPARPAINING WAXED PETROLEUM PRODUCTS |
| JPH07116454A (en) | 1993-10-21 | 1995-05-09 | Babcock Hitachi Kk | Process and device for desulfurizing exhaust gas |
| JPH07316567A (en) * | 1994-05-23 | 1995-12-05 | Mitsubishi Oil Co Ltd | Dewaxing of lubricating oil fraction and dewaxing assistant |
| JP2000336377A (en) * | 1999-03-25 | 2000-12-05 | Sanyo Chem Ind Ltd | De-waxing assistant |
| JP4920817B2 (en) * | 1999-09-20 | 2012-04-18 | 三洋化成工業株式会社 | Dewaxing aid |
| JP2001164268A (en) | 1999-12-09 | 2001-06-19 | Toho Chem Ind Co Ltd | New dewaxing auxiliary |
| JP4900997B2 (en) | 2000-09-21 | 2012-03-21 | 東邦化学工業株式会社 | New dewaxing aid |
| JP2002097477A (en) | 2000-09-21 | 2002-04-02 | Toho Chem Ind Co Ltd | Novel dewaxing method |
| JP2003003176A (en) | 2001-06-22 | 2003-01-08 | Toho Chem Ind Co Ltd | New dewaxing auxiliary |
-
2002
- 2002-02-22 JP JP2002093268A patent/JP3841404B2/en not_active Expired - Lifetime
- 2002-10-25 US US10/504,685 patent/US7388122B2/en not_active Expired - Fee Related
- 2002-10-25 WO PCT/JP2002/011100 patent/WO2003070858A1/en active Application Filing
- 2002-10-25 AU AU2002344578A patent/AU2002344578A1/en not_active Abandoned
- 2002-10-25 EP EP02777955A patent/EP1486553A4/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002097478A (en) * | 2000-09-21 | 2002-04-02 | Toho Chem Ind Co Ltd | Novel dewaxing auxiliary |
Also Published As
| Publication number | Publication date |
|---|---|
| US7388122B2 (en) | 2008-06-17 |
| JP3841404B2 (en) | 2006-11-01 |
| WO2003070858A1 (en) | 2003-08-28 |
| EP1486553A4 (en) | 2011-10-26 |
| EP1486553A1 (en) | 2004-12-15 |
| US20050054775A1 (en) | 2005-03-10 |
| AU2002344578A1 (en) | 2003-09-09 |
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